WO2021205841A1 - Container for cold storage of agricultural or horticultural crop - Google Patents

Container for cold storage of agricultural or horticultural crop Download PDF

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Publication number
WO2021205841A1
WO2021205841A1 PCT/JP2021/011186 JP2021011186W WO2021205841A1 WO 2021205841 A1 WO2021205841 A1 WO 2021205841A1 JP 2021011186 W JP2021011186 W JP 2021011186W WO 2021205841 A1 WO2021205841 A1 WO 2021205841A1
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WO
WIPO (PCT)
Prior art keywords
agricultural
container
film
storage
horticultural crops
Prior art date
Application number
PCT/JP2021/011186
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French (fr)
Japanese (ja)
Inventor
麻里江 西村
茂美 瀬尾
嘉彦 足立
小塚　明彦
朗 辻
貴章 田中
Original Assignee
国立研究開発法人農業・食品産業技術総合研究機構
小島プレス工業株式会社
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Application filed by 国立研究開発法人農業・食品産業技術総合研究機構, 小島プレス工業株式会社 filed Critical 国立研究開発法人農業・食品産業技術総合研究機構
Priority to CN202180021916.3A priority Critical patent/CN115298113A/en
Publication of WO2021205841A1 publication Critical patent/WO2021205841A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B7/00—Preservation or chemical ripening of fruit or vegetables
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/18—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents providing specific environment for contents, e.g. temperature above or below ambient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/28—Applications of food preservatives, fungicides, pesticides or animal repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/50—Containers, packaging elements or packages, specially adapted for particular articles or materials for living organisms, articles or materials sensitive to changes of environment or atmospheric conditions, e.g. land animals, birds, fish, water plants, non-aquatic plants, flower bulbs, cut flowers or foliage

Definitions

  • the present invention relates to a container for low temperature storage of agricultural and horticultural crops provided with a sustained release antibacterial film, a package containing agricultural and horticultural crops, and a method for low temperature storage of agricultural and horticultural crops.
  • hypochlorous acid-based disinfectants are handled. There were problems such as the need for a high degree of caution and the inability to obtain long-term effects.
  • a method for imparting antibacterial performance to a resin film or the like used for packaging agricultural or horticultural crops a method of coating the surface of the film with a vaporizable antibacterial agent (for example, Patent Document 2 or the like) or a resin is used.
  • a method of kneading an inorganic antibacterial agent or an organic antibacterial agent for example, Patent Documents 3 and 4 and the like.
  • the former coating method it is difficult to control the amount of antibacterial agent that vaporizes from the antibacterial film, and when the vaporization concentration of the antibacterial agent becomes high, the odor is transferred to the packaged agricultural and horticultural crops, and quality deterioration such as discoloration occurs. May lead to.
  • the latter method of kneading produces antibacterial activity only in the portion in contact with the antibacterial agent exposed on the surface of the antibacterial film, so that it is difficult to express the antibacterial activity in the entire packaged agricultural and horticultural crops, and the inside of the resin.
  • the antibacterial agent existing in the above cannot exhibit the antibacterial activity, and a large amount of the antibacterial agent is required to obtain the desired antibacterial activity.
  • the present invention is a new invention suitable for distribution and storage, which reliably suppresses a significant decrease in the commercial value of agricultural and horticultural crops due to mold, does not cause odor transfer due to antibacterial active ingredients, and does not cause quality deterioration such as discoloration.
  • the challenge is to provide new containers, new packaging, and new storage methods.
  • the present inventor has set the volume of the storage container, the area of the sustained-release antibacterial film, and the ratio of both within a specific range to improve the quality of agricultural and horticultural crops. It was found that the significant decrease in the commercial value of agricultural and horticultural crops due to mold can be surely suppressed without reducing the above-mentioned problems, and the above-mentioned problems have been solved.
  • the gist of the present invention is as follows. 1.
  • a volatile antibacterial active ingredient consisting of a base film layer, a volatile antibacterial active ingredient layer containing at least one selected from a group of volatile antibacterial active compounds having a boiling point in the range of 100 to 240 ° C., and a vaporized polymer film.
  • a container for low-temperature storage of agricultural and horticultural crops which comprises a sustained-release antibacterial film formed by laminating transparent layers in this order and which satisfies the following requirements 1 to 3.
  • volume of storage container is 25 cm 3 or more 250,000Cm 3 or less.
  • [Requirement 2] the area of the sustained release antimicrobial film is 1 cm 2 or more 5,000 cm 2 or less.
  • the volatile antibacterial active ingredient permeable layer is composed of a vapor-deposited polymerized film, a specific volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer. It is possible to stably release the active compound, and the volume of the storage container (requirement 1) and the area of the sustained-release antibacterial film (requirement 2) are within a specific range, and the volume is further increased. By setting the area ratio to a specific value or more (Requirement 3), the amount of volatilized antibacterial active ingredient in the storage container can be made appropriate.
  • the present invention can surely suppress a significant decrease in the commercial value of the agricultural and horticultural crops due to mold without deteriorating the quality of the agricultural and horticultural crops. Since the volatile antibacterial active compound having a specific boiling point range used in the present invention is also a plant aroma component used as a food additive, the present invention is useful in that agricultural and horticultural crops can be safely preserved. ..
  • the container for low-temperature storage of agricultural and horticultural crops in the present invention and the method for preserving agricultural and horticultural crops using the container will be described in detail.
  • the "low temperature” in the present invention means a temperature range of -3 ° C or higher and 15 ° C or lower.
  • the container for low-temperature storage of agricultural and horticultural crops in the present invention is a container for storing agricultural and horticultural crops.
  • the agricultural and horticultural crops in the present invention mean all cultivated crops such as ordinary crops, vegetables, fruits, flowers, fungi and mushrooms.
  • Agricultural and horticultural crops are not particularly limited, but for example, ordinary crops such as paddy rice, wheat, corn, potatoes and beans, root vegetables such as radish, carrot and gobo, and stem vegetables such as onion, asparagus and udo.
  • ordinary crops such as paddy rice, wheat, corn, potatoes and beans, root vegetables such as radish, carrot and gobo, and stem vegetables such as onion, asparagus and udo.
  • fruits such as cherry blossoms and peaches, flowers such as cut flowers, and cauliflowers such as shimeji mushrooms, pine bamboo, and radish.
  • the agricultural and horticultural crops in the present invention are suitable for fruits, and above all, grapes, cherries, peaches and strawberries.
  • grapes, cherries, peaches and strawberries a temperature range of 0 ° C. or higher and 5 ° C. or lower is a more preferable storage temperature.
  • volatile antibacterial active ingredient one or more selected from the group of volatile antibacterial active compounds having a boiling point in the range of 100 to 240 ° C. is used as the volatile antibacterial active ingredient.
  • the compounds contained in the volatile antibacterial active compound group of the present invention preferably have a constituent carbon atoms in the range of 5 or more and 10 or less, and specific examples of suitable compounds include, for example, hinokithiol (boiling point:: 140 ° C), citronellal (boiling point: 204-206 ° C), green leaf aldehyde (trans-2-hexenal, boiling point: 146 ° C), citronellol (boiling point: 225 ° C), geraniol (boiling point: 229 ° C), nerol (boiling point: 224 ° C).
  • volatile antibacterial active compounds having a boiling point in the range of 100 to 200 ° C. are preferable, and hinokitiol and green leaf aldehyde are particularly preferable.
  • the volatile antibacterial active ingredient layer of the present invention a method according to the form and properties of the volatile antibacterial active ingredient to be used can be appropriately selected. For example, if it is a volatile antibacterial active ingredient that is liquid at room temperature, it can be applied as it is on one surface of the base film layer without being diluted to form a volatile antibacterial active ingredient layer. Even if it is a volatile antibacterial active ingredient that is solid at room temperature or a volatile antibacterial active ingredient that is liquid at room temperature, a solution is prepared with a predetermined solvent, for example, ethanol, and the solution is placed on one surface of the base film layer. By coating and evaporating the solvent, a volatile antibacterial active ingredient layer consisting substantially only of the volatile antibacterial active ingredient can be formed.
  • a predetermined solvent for example, ethanol
  • a volatile antibacterial active ingredient layer composed of only the volatile antibacterial active ingredient is formed.
  • the vaporization treatment method can also be selected.
  • the thickness of the volatile antibacterial active ingredient layer in the present invention may be appropriately determined depending on the type of the volatile antibacterial active ingredient to be selected and the desired antibacterial activity maintenance period, but is usually in the range of 1 ⁇ m or more and 5 mm or less.
  • the volatile antibacterial active ingredient permeable layer in the present invention is made of a vapor-deposited polymerized film.
  • the thin-film deposition polymer film means a thin film obtained according to the thin-film deposition polymerization method.
  • the thin-film polymerization film generally, two or more kinds of raw material monomers vaporized by heating are introduced into a film forming chamber in a vacuum state and adhered to the surface of a film forming object arranged in the film forming chamber. It is formed by advancing polymerization between raw material monomers on such a surface.
  • the formation of the film proceeds while following the fine irregularities existing on the surface of the volatile antibacterial active ingredient layer in the present invention, so that the volatile antibacterial active ingredient permeable layer is formed. It exhibits excellent adhesion between the active ingredient layer and the volatile antibacterial active ingredient permeation layer.
  • the thin-film vapor-deposited polymer film can be produced even with an extremely thin film thickness, and the obtained thin-film polymer film also has an advantage that the content of impurities is very small. Therefore, in the sustained release antibacterial film of the present invention, the occurrence of delamination due to hydrolysis, heat shock, etc. is advantageously suppressed between the volatilized antibacterial active ingredient layer and the volatilized antibacterial active ingredient permeation layer. Therefore, it is possible to stably release and volatilize the amount of volatilizing antibacterial active ingredient according to the purpose.
  • the synthetic resin constituting the volatile antibacterial active ingredient permeable layer in the present invention among synthetic resins capable of forming a film according to a conventionally known vapor deposition polymerization method, those corresponding to the volatile antibacterial active ingredient are appropriately used. You can choose.
  • the synthetic resin film constituting the volatile antibacterial active ingredient permeable layer includes a polyurea resin film, a polyamide resin film, a polyimide resin film, a polyamideimide resin film, a polyester resin film, a polyazomethine resin film, and a polyurethane resin film.
  • Various synthetic resin films that can be produced according to a known vapor deposition polymerization method such as, etc. can be exemplified.
  • the polyyuria resin film can be advantageously adopted because it has a crosslinked structure in which the volatile antibacterial active ingredient can be effectively permeated.
  • the thickness of the volatile antibacterial active ingredient permeation layer is the amount of the volatile antibacterial active ingredient released to the outside of the film per unit time, and the type and amount of the volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer. Etc. can be comprehensively considered and determined as appropriate.
  • the thickness of the volatile antibacterial active ingredient permeation layer is preferably in the range of 0.01 ⁇ m or more and 50 ⁇ m or less, and more preferably in the range of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the sustained-release antibacterial film in the present invention has a volatile antibacterial active ingredient layer formed on one surface of the base film layer, and further comprises a vapor-deposited polymerized film on the surface of the volatile antibacterial active ingredient layer. It is preferable that the volatile antibacterial active ingredient permeable layer is formed, and the sizes of the base film layer, the volatile antibacterial active ingredient layer and the volatile antibacterial active ingredient permeable layer are substantially the same.
  • the sustained release antibacterial film in the present invention is preferably placed on the upper part of the container for low temperature storage of agricultural and horticultural crops, and is arranged by covering the surface of the agricultural and horticultural crop inside the container or by sticking to the top surface of the container. Is more preferable.
  • the volatile antibacterial active ingredient permeation layer in the sustained release antibacterial film is arranged so as to face the agricultural and horticultural crops inside the container.
  • Agricultural and horticultural crops cryopreservation container according to the present invention the "requirement 2" and is characterized in that it comprises 1 cm 2 or more 5,000 cm 2 or less sustained release antimicrobial film.
  • Area of the sustained release antimicrobial film preferably has 5 cm 2 or more 1,000 cm 2 or less, and more preferably from 10 cm 2 or more 500 cm 2 or less.
  • the sustained release antibacterial film provided in the container for low temperature storage of agricultural and horticultural crops of the present invention may be one sheet, or two or more sheets may be used. When a plurality of sheets are used, the area of the sustained release antibacterial film in the present invention means the total area of all the sustained release antibacterial films used.
  • the container for low-temperature storage of agricultural and horticultural crops of the present invention is not particularly limited in terms of materials such as resin and paper, and shapes such as bag shape and box shape, but among them, box-shaped containers are preferable. However, it is preferable that the container can be sealed to some extent so that the amount of the volatilized antibacterial active ingredient volatilized from the sustained release antibacterial film in the present invention can be maintained.
  • the container for low-temperature storage of agricultural and horticultural crops of the present invention may be a container made of the sustained-release antibacterial film of the present invention, but a bag made of a material different from the sustained-release antibacterial film of the present invention.
  • Agricultural and horticultural crops cryopreservation container according to the present invention, the "requirement 1", and is characterized in that its volume is 25 cm 3 or more 250,000Cm 3 or less.
  • the volume of storage container preferably has a 500 cm 3 or more 100,000 3 or less, 1000 cm 3 or more 50,000 cm 3 less is more preferable.
  • the amount of the volatile antibacterial active ingredient in the storage container can be adjusted to an appropriate level. It is possible to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold without deteriorating the quality.
  • the amount of antibacterial component in the container increases with the passage of time. If the amount of antibacterial ingredient in the container is too small, sufficient antibacterial activity cannot be obtained and the agricultural and horticultural crops will rot. The commercial value of agricultural and horticultural crops will decline.
  • the present invention can control the amount of antibacterial component in the storage container within an appropriate range, and the area of the sustained-release antibacterial film required for that purpose, the range of the volume of the storage container, and the sustained-release antibacterial film. This is the first time that the relationship with the storage container has been identified.
  • the volatile antibacterial active ingredient in the present invention may be one or more selected from the volatile antibacterial active compound group having a boiling point in the range of 100 to 240 ° C. It is one of the requirements that makes it possible to make it proper. As described above, by optimizing the amount of volatile antibacterial active ingredient in the container for low temperature storage of agricultural and horticultural crops of the present invention, it is possible to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold, and also. It can be used as a container for low-temperature storage of agricultural and horticultural crops suitable for distribution and storage without causing quality deterioration such as discoloration in addition to odor transfer due to antibacterial active ingredients.
  • a volatile antibacterial active ingredient layer was formed so as to have a concentration of 1.3 mg / cm 2.
  • a thin-film polymer film made of a polyureia resin was produced using the same thin-film polymer film-forming apparatus.
  • the thin-film polymerized film made of polyureia resin was prepared with a thickness of 4 ⁇ m.
  • ⁇ Test 1 for low temperature storage of agricultural and horticultural crops As a storage container, a closed container 1 with an insole colander (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm ⁇ 134 mm, height: outer dimensions 77 mm) was used. As shown in FIG. 1, a paper towel soaked in distilled water (20 mL) is laid on the bottom surface of the storage container so that the humidity can be maintained (1 in FIG. 1), and a packaging sponge is placed on the insole colander. (2 in FIG. 1), a sustained-release antibacterial film 1 (area: 78 cm 2 ) prepared inside the lid of the storage container was attached with double-sided tape (3 in FIG. 1) and used.
  • the storage container has "Requirement 3" in the present invention of about 0.071. Shine Muscat berries were used as the agricultural and horticultural crops to be preserved. As shown in FIG. 1, 12 grains were placed in an insole colander on which a packaging sponge was placed (as shown in 4 in FIG. 1), sterilized water was sprayed, and then air-dried was used. This was set to 1 in FIG. 1 and the lid (3 in FIG. 1) was closed, and a preservation test was conducted as Example 1. A similar storage test was performed using a storage container that differs only in that it does not use a sustained release antibacterial film as Comparative Example 1. The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation. The storage test was carried out three times each, and the average value of the cumulative spoilage rate (%) was calculated. Table 1 summarizes the test results at a storage temperature of 5 ° C.
  • the container for low-temperature storage of agricultural and horticultural crops (Example 1) of the present invention had no putrefactive fruits even after 70 days (2.5 months) from the start of storage, and 91 days from the start of storage.
  • the average cumulative spoilage rate after (3 months or more) was 11.1%.
  • no quality deterioration such as odor transfer or discoloration due to the volatile antibacterial active ingredient was confirmed in the fruit grains 91 days after the start of storage.
  • a storage container different from that of the present invention was used (Comparative Example 1)
  • the average cumulative spoilage rate was 8.3% after 21 days (3 weeks) from the start of storage. After 91 days (3 months or more), it reached 69.4%.
  • ⁇ Test 2 for low temperature storage of agricultural and horticultural crops 12 fruit grains in a closed container 1 (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm x 134 mm, height: outer dimensions 77 mm) with an inlay colander, which is the same as the above "Test 1 for low temperature storage of agricultural and horticultural crops”.
  • Sustained release of antibacterial film 1 area: 78 cm 2
  • a similar container 2 (capacity: 5,000 cm 3 , bottom size: outer dimensions 213 mm x 263 mm, height: outer dimensions 130 mm) with 25 fruit grains.
  • the sex antibacterial film 2 (area: 312 cm 2 ) was set in the same manner as in the above-mentioned "Test 1 on low temperature storage of agricultural and horticultural crops".
  • a suspension of Botrytis cinerea conidia (106 cells / mL) was spray-inoculated, and then a preservation test was conducted at a preservation temperature of 5 ° C. using air-dried Shine Muscat berries.
  • the humidity was maintained in the container 1 (Example 2 and Comparative Example 2) using distilled water (20 mL) and in the container 2 (Example 3 and Comparative Example 3) using distilled water (100 mL).
  • Example 2 The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
  • the storage test was carried out 5 times in Example 2 and Comparative Example 2, and 4 times in Example 3 and Comparative Example 3, and the average value of the cumulative putrefaction rate (%) was calculated. Table 2 summarizes the test results.
  • test 2 on low temperature storage of agricultural and horticultural crops is a preservation test that imitates a very harsh environment in which Botrytis cinerea is forcibly inoculated.
  • Table 2 in Comparative Example 2 which is a storage container different from the present invention, in Comparative Example 3 in which all the test berries are also different from the present invention on the 28th day from the start of storage. , 98% of the test grains rotted.
  • the decay of the agricultural and horticultural crop by mold is approximately 5 minutes of the test fruit grains.
  • Example 3 it was found that 6% of the test berries were extremely excellent in the effect of suppressing spoilage. Further, it was clarified that this excellent anti-corruption effect is exhibited regardless of the difference in the volume of the storage container of "Requirement 1". In addition, no quality deterioration such as odor transfer or discoloration due to the antibacterial active ingredient was confirmed in the berries 28 days after the start of storage of Examples 2 and 3.
  • ⁇ Test 3 for low temperature storage of agricultural and horticultural crops 12 fruit grains in a closed container 1 (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm x 134 mm, height: outer dimensions 77 mm) with an inlay colander, which is the same as the above "Test 1 for low temperature storage of agricultural and horticultural crops”.
  • the sustained release antibacterial film 1 area: 78 cm 2
  • the sustained release antibacterial film 3 area: 39 cm 2
  • the sustained release antibacterial film 4 area: 19 cm 2
  • the film was set in the same manner as in "Test 1", and the humidity was maintained using distilled water (20 mL).
  • a suspension of Botrytis cinerea conidia 106 cells / mL was spray-inoculated, and then a preservation test was conducted at a temperature of 5 ° C. using air-dried Shine Muscat grains.
  • the plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
  • the storage test was carried out four times each, and the average value of the cumulative spoilage rate (%) was calculated. Table 3 summarizes the test results.
  • test 3 on low temperature storage of agricultural and horticultural crops is a preservation test that imitates a very harsh environment in which Botrytis cinerea is forcibly inoculated.
  • Table 3 in Comparative Example 5, which is a storage container different from the present invention, 97.9% of the test berries were putrefactive on the 28th day from the start of storage.
  • the decay of agricultural and horticultural crops due to mold is 70 days from the start of storage (Examples 4 and 5).
  • Comparative Example 4 has "Requirement 3" in the present invention, that is, the ratio of the area of the sustained release antibacterial film (cm 2 ) to the volume of the storage container (cm 3 ) is about 0.017. It differs from the storage container of the invention. Therefore, in the preservation in Comparative Example 4, it was confirmed that the progress of mold rot of agricultural and horticultural crops after the 28th day from the start of preservation progressed to about 2.5 to 4 times that of the Example.
  • ⁇ Test 4 for low temperature storage of agricultural and horticultural crops Put 41 berries in a closed container 3 with an inoculation colander (capacity: 0.0030 m 3 , bottom size: outer dimensions 239 mm x 176 mm, height: outer dimensions 91 mm), and release the sustained-release antibacterial film 5 (area: 233 cm 2). ), Sustained release antibacterial film 1 (area: 78 cm 2 ), spray-inoculated with sterilized water (no inoculation), and then air-dried fruit grains in the same manner as in "Test 1 for low-temperature storage of agricultural and horticultural crops”.
  • the humidity of the container 3 was maintained by using distilled water (60 mL).
  • the plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted.
  • the rotten fruit was removed at the time of observation confirmation.
  • the storage test was carried out three times each, and the average value of the cumulative spoilage rate (%) was calculated.
  • Table 4 summarizes the test results. In Comparative Examples 8 and 9, the results on the 21st day from the start of storage showed a large difference from Examples 6 and 7, so it was judged that no further follow-up was necessary, and the test was terminated. “-” In Table 4 means that the test observation was not performed.
  • the container for low-temperature storage of agricultural and horticultural crops (Examples 6 and 7) of the present invention is different from that of the present invention in non-inoculation storage of gray mold fungi imitating a general storage state. It was clarified that the effect of suppressing mold spoilage of agricultural and horticultural crops was extremely excellent as compared with the containers for use (Comparative Examples 6 and 7). In addition, no quality deterioration such as odor transfer or discoloration due to the antibacterial active ingredient was confirmed in the berries 28 days after the start of storage of Examples 6 and 7.
  • the volatile antibacterial active ingredient permeable layer is composed of a vapor-deposited polymerized film
  • a specific volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer It is possible to stably release the active compound, and the volume of the storage container (requirement 1) and the area of the sustained-release antibacterial film (requirement 2) are within a specific range, and the volume is further increased.
  • the area ratio By setting the area ratio to a specific value or more (Requirement 3), the amount of volatilized antibacterial active ingredient in the storage container can be made appropriate. Due to these synergistic effects, it is very useful because it is possible to surely suppress a significant decrease in the commercial value of the agricultural and horticultural crops due to mold without deteriorating the quality of the agricultural and horticultural crops.

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

The present invention addresses the problem of providing a novel container suitable for transportation and storage, said container reliably suppressing serious reduction of the marketability of an agricultural or horticultural crop caused by molds while preventing smell migration due to an antimicrobial active component, coloration and quality deterioration, a novel package and a novel storage method. As a means for solving the problem, provided is a container for cold storage of an agricultural or horticultural crop, said container being provided with a sustained-release antimicrobial film that comprises a substrate film layer, a volatile antimicrobial active component layer containing one or more compounds selected from the group consisting of volatile antimicrobial active compounds having a boiling point within the range of 100-240°C, and a volatile antimicrobial active component-permeable layer formed of a vapor deposition-polymerized film, these layers being laminated in this order. This container satisfies the following requirements 1 to 3. [Requirement 1] The volume of the storage container is 25 cm3 to 250,000 cm3 inclusive. [Requirement 2] The area of the sustained-release antimicrobial film is 1 cm2 to 5,000 cm2 inclusive. [Requirement 3] To the volume (cm3) of the storage container, the ratio of the area (cm2) of the sustained-release antimicrobial film is 0.02 or greater.

Description

農園芸作物低温保存用容器Container for low temperature storage of agricultural and horticultural crops
　本発明は、徐放性抗菌フィルムを備える農園芸作物低温保存用容器、農園芸作物入り包装体および、農園芸作物の低温保存方法に関する。 The present invention relates to a container for low temperature storage of agricultural and horticultural crops provided with a sustained release antibacterial film, a package containing agricultural and horticultural crops, and a method for low temperature storage of agricultural and horticultural crops.
　従来、収穫された普通作物、野菜類、果物類、花卉類、菌茸等といった農園芸作物の長期保存方法として、脱酸素剤の同封などにより農園芸作物の呼吸を適度に抑制する方法や、０℃以下の氷温で保存する方法などが知られている（例えば、特許文献１等）が、これらの方法では、カビの発生を抑制することができないという問題があった。国内では、農園芸作物の流通時に殺菌剤等の農薬の使用は認められておらず、欧州などの海外でもその使用には大きな制限がある。そのため、農園芸作物の防カビ方法として、収穫された農園芸作物を予め次亜塩素酸系の消毒剤で殺菌処理する手法が知られているが、次亜塩素酸系の消毒剤は取扱に高度な注意が必要であり、長期間の効果が得られないなどの問題があった。 Conventionally, as a long-term storage method for agricultural and horticultural crops such as harvested ordinary crops, vegetables, fruits, flowers, fungi, etc., a method of appropriately suppressing the respiration of agricultural and horticultural crops by enclosing a deoxidizer, etc. There are known methods of storing at an ice temperature of 0 ° C. or lower (for example, Patent Document 1 and the like), but these methods have a problem that the growth of mold cannot be suppressed. In Japan, the use of pesticides such as fungicides is not permitted during the distribution of agricultural and horticultural crops, and there are major restrictions on their use overseas, such as in Europe. Therefore, as a method for preventing mold on agricultural and horticultural crops, a method of sterilizing harvested agricultural and horticultural crops in advance with a hypochlorous acid-based disinfectant is known, but hypochlorous acid-based disinfectants are handled. There were problems such as the need for a high degree of caution and the inability to obtain long-term effects.
　一方、農園芸作物の包装に使用する樹脂製フィルム等に、抗菌性能を付与するための方法として、当該フィルム表面に気化性抗菌剤を被覆する方法（例えば、特許文献２等）や、樹脂に無機系抗菌剤や有機系抗菌剤を練り込む方法（例えば、特許文献３、４等）が知られている。前者の被覆する方法は、抗菌フィルムから気化する抗菌剤の量をコントロールすることが難しく、抗菌剤の気化濃度が高くなると、包装された農園芸作物への匂い移りのほか、変色などの品質劣化を招く恐れがある。また、後者の練り込む方法は、抗菌フィルムの表面に露出した抗菌剤と接触した部分に限り抗菌活性が生じるため、包装された農園芸作物全体への抗菌活性の発現が難しいことや、樹脂内部に存在する抗菌剤は抗菌活性を発揮し得ず、所望の抗菌活性を得るためには、多量の抗菌剤が必要になるという問題があった。 On the other hand, as a method for imparting antibacterial performance to a resin film or the like used for packaging agricultural or horticultural crops, a method of coating the surface of the film with a vaporizable antibacterial agent (for example, Patent Document 2 or the like) or a resin is used. A method of kneading an inorganic antibacterial agent or an organic antibacterial agent (for example, Patent Documents 3 and 4 and the like) is known. With the former coating method, it is difficult to control the amount of antibacterial agent that vaporizes from the antibacterial film, and when the vaporization concentration of the antibacterial agent becomes high, the odor is transferred to the packaged agricultural and horticultural crops, and quality deterioration such as discoloration occurs. May lead to. In addition, the latter method of kneading produces antibacterial activity only in the portion in contact with the antibacterial agent exposed on the surface of the antibacterial film, so that it is difficult to express the antibacterial activity in the entire packaged agricultural and horticultural crops, and the inside of the resin. There is a problem that the antibacterial agent existing in the above cannot exhibit the antibacterial activity, and a large amount of the antibacterial agent is required to obtain the desired antibacterial activity.
特開平０６－０４６７４９号公報Japanese Unexamined Patent Publication No. 06-046749 特開２００６－１９９８５２号公報Japanese Unexamined Patent Publication No. 2006-199852 特開２０１６－０３０４０６号公報Japanese Unexamined Patent Publication No. 2016-030406 特開２０１５－１８９１３８号公報Japanese Unexamined Patent Publication No. 2015-189138
　本発明は、カビによる農園芸作物の商品価値の著しい低下を確実に抑制し、かつ、抗菌活性成分による匂い移りのほか、変色などの品質劣化をさせることのない、流通や保存に適した新たな容器、新たな包装体さらには、新たな保存方法を提供することを課題としている。 The present invention is a new invention suitable for distribution and storage, which reliably suppresses a significant decrease in the commercial value of agricultural and horticultural crops due to mold, does not cause odor transfer due to antibacterial active ingredients, and does not cause quality deterioration such as discoloration. The challenge is to provide new containers, new packaging, and new storage methods.
　本発明者は上記課題を解決するために鋭意研究を重ねた結果、保存用容器の容積と徐放性抗菌フィルムの面積および、両者の比を特定の範囲とすることにより、農園芸作物の品質を低下させることなく、カビによる農園芸作物の商品価値の著しい低下を確実に抑制できることを見出し、上記課題を解決するに至ったものである。 As a result of intensive research to solve the above problems, the present inventor has set the volume of the storage container, the area of the sustained-release antibacterial film, and the ratio of both within a specific range to improve the quality of agricultural and horticultural crops. It was found that the significant decrease in the commercial value of agricultural and horticultural crops due to mold can be surely suppressed without reducing the above-mentioned problems, and the above-mentioned problems have been solved.
　本発明は、具体的には次の事項を要旨とする。
１．基材フィルム層と、沸点が１００～２４０℃の範囲にある揮散性抗菌活性化合物群から選択される１種以上を含有する揮散性抗菌活性成分層と、蒸着重合膜からなる揮散性抗菌活性成分透過層を、この順で積層してなる徐放性抗菌フィルムを備え、かつ、下記要件１～３を満たす農園芸作物低温保存用容器。
［要件１］；保存用容器の容積が２５ｃｍ３以上２５０，０００ｃｍ３以下である。
［要件２］；徐放性抗菌フィルムの面積が１ｃｍ２以上５，０００ｃｍ２以下である。
［要件３］；保存用容器の容積（ｃｍ３）に対する、徐放性抗菌フィルムの面積（ｃｍ２）の比が、０．０２以上である。
２．１．に記載の低温保存用容器に農園芸作物を収容してなる、農園芸作物収容包装体。
３．１．に記載の保存用容器を用いて農園芸作物を収容して、－３℃以上１５℃以下で保存する、農園芸作物の保存方法。 Specifically, the gist of the present invention is as follows.
1. 1. A volatile antibacterial active ingredient consisting of a base film layer, a volatile antibacterial active ingredient layer containing at least one selected from a group of volatile antibacterial active compounds having a boiling point in the range of 100 to 240 ° C., and a vaporized polymer film. A container for low-temperature storage of agricultural and horticultural crops, which comprises a sustained-release antibacterial film formed by laminating transparent layers in this order and which satisfies the following requirements 1 to 3.
[Requirement 1]; volume of storage container is 25 cm 3 or more 250,000Cm 3 or less.
[Requirement 2]; the area of the sustained release antimicrobial film is 1 cm 2 or more 5,000 cm 2 or less.
[Requirement 3]; The ratio of the area of the sustained release antibacterial film (cm 2 ) to the volume of the storage container (cm 3 ) is 0.02 or more.
2.1. A farming and horticultural crop storage package for storing agricultural and horticultural crops in the low-temperature storage container described in 1.
3.1. A method for preserving agricultural and horticultural crops, wherein the agricultural and horticultural crops are stored in the storage container described in the above and stored at -3 ° C or higher and 15 ° C or lower.
　本発明の容器に備えられている徐放性抗菌フィルムは、揮散性抗菌活性成分透過層が蒸着重合膜により構成されていることから、揮散性抗菌活性成分層に含有される特定の揮散性抗菌活性化合物を安定的に放出させることが可能であり、保存用容器の容積（要件１）と当該徐放性抗菌フィルムの面積（要件２）とを特定の範囲のものとし、さらに当該容積に対する当該面積の比を特定の数値以上（要件３）とすることにより、保存用容器内の揮散した抗菌活性成分量を適正なものとすることができる。本発明は、これらの相乗効果により、農園芸作物の品質を低下させることなく、カビによる農園芸作物の商品価値の著しい低下を確実に抑制することができる。
　本発明において使用する、特定の沸点範囲を有する揮散性抗菌活性化合物は、食品添加物として使用される植物香気成分でもあるため、農園芸作物を安全に保存できる点において、本発明は有用である。 In the sustained-release antibacterial film provided in the container of the present invention, since the volatile antibacterial active ingredient permeable layer is composed of a vapor-deposited polymerized film, a specific volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer. It is possible to stably release the active compound, and the volume of the storage container (requirement 1) and the area of the sustained-release antibacterial film (requirement 2) are within a specific range, and the volume is further increased. By setting the area ratio to a specific value or more (Requirement 3), the amount of volatilized antibacterial active ingredient in the storage container can be made appropriate. Due to these synergistic effects, the present invention can surely suppress a significant decrease in the commercial value of the agricultural and horticultural crops due to mold without deteriorating the quality of the agricultural and horticultural crops.
Since the volatile antibacterial active compound having a specific boiling point range used in the present invention is also a plant aroma component used as a food additive, the present invention is useful in that agricultural and horticultural crops can be safely preserved. ..
実施例の農園芸作物低温保存に関する試験１における、保存試験を実施した容器の構成１～４を説明する写真図である。It is a photographic figure explaining the structure 1 to 4 of the container which carried out the preservation test in the test 1 concerning the low temperature preservation of agricultural and horticultural crops of an Example.
　以下、本発明における農園芸作物低温保存用容器や、当該容器を用いた農園芸作物の保存方法について詳細に説明する。なお、本発明における「低温」は、－３℃以上１５℃以下の温度範囲を意味する。
＜農園芸作物について＞
　本発明における農園芸作物低温保存用容器は、農園芸作物を保存するための容器である。ここで、本発明における農園芸作物とは、普通作物、野菜類、果物類、花卉類、菌茸類等の栽培作物全般を意味する。農園芸作物としては、特に限定されないが、例えば、水稲、麦類、トウモロコシ、イモ類、マメ類などの普通作物、ダイコン、ニンジン、ゴボウ等の根菜類、タマネギ、アスパラガス、ウド等の茎菜類、キャベツ、レタス、ホウレンソウ、ハクサイ等の葉菜類、トマト、ナス、カボチャ等の果菜類、カリフラワー、ブロッコリー、食用菊等の花菜類などの野菜類、柑橘、リンゴ、ナシ、ブドウ、ブルーベリー、イチゴ、桜桃、桃等の果物類、切り花などの花卉類、シメジ、マツタケ、マイタケ等の菌茸類が挙げられる。
　中でも、冷温保存に適し、効果的にカビ発生抑制効果を得る観点から、本発明における農園芸作物としては、果物類において好適であり、中でも、ブドウ、桜桃、桃、イチゴにおいてより好適である。ブドウ、桜桃、桃、イチゴについては、０℃以上５℃以下の温度範囲がより好適な保存温度である。 Hereinafter, the container for low-temperature storage of agricultural and horticultural crops in the present invention and the method for preserving agricultural and horticultural crops using the container will be described in detail. The "low temperature" in the present invention means a temperature range of -3 ° C or higher and 15 ° C or lower.
<About agricultural and horticultural crops>
The container for low-temperature storage of agricultural and horticultural crops in the present invention is a container for storing agricultural and horticultural crops. Here, the agricultural and horticultural crops in the present invention mean all cultivated crops such as ordinary crops, vegetables, fruits, flowers, fungi and mushrooms. Agricultural and horticultural crops are not particularly limited, but for example, ordinary crops such as paddy rice, wheat, corn, potatoes and beans, root vegetables such as radish, carrot and gobo, and stem vegetables such as onion, asparagus and udo. Kinds, cabbage, lettuce, spinach, Chinese cabbage and other leafy vegetables, tomatoes, eggplants, pumpkins and other fruit vegetables, cauliflower, broccoli, edible chrysanthemum and other vegetable vegetables, citrus, apples, pears, grapes, blueberries, strawberries, Examples include fruits such as cherry blossoms and peaches, flowers such as cut flowers, and cauliflowers such as shimeji mushrooms, pine bamboo, and radish.
Above all, from the viewpoint of being suitable for cold storage and effectively obtaining the effect of suppressing mold growth, the agricultural and horticultural crops in the present invention are suitable for fruits, and above all, grapes, cherries, peaches and strawberries. For grapes, cherries, peaches and strawberries, a temperature range of 0 ° C. or higher and 5 ° C. or lower is a more preferable storage temperature.
＜揮散性抗菌活性成分について＞
　本発明は、沸点が１００～２４０℃の範囲にある揮散性抗菌活性化合物群から選択される１種以上を、揮散性抗菌活性成分とするものである。
　本発明の揮散性抗菌活性化合物群に含まれる化合物としては、構成する炭素原子数は５個以上１０個以下の範囲のものが好ましく、好適な化合物の具体例としては、例えば、ヒノキチオール（沸点：１４０℃）、シトロネラール（沸点：２０４～２０６℃）、青葉アルデヒド（トランス－２－ヘキセナール、沸点：１４６℃）、シトロネロール（沸点：２２５℃）、ゲラニオール（沸点：２２９℃）、ネロール（沸点：２２４～２２５℃／７４５ｍｍＨｇ）等が挙げられる。中でも、沸点が１００～２００℃の範囲にある揮散性抗菌活性化合物が好ましく、特に、ヒノキチオール、青葉アルデヒドが好ましい。 <About volatile antibacterial active ingredient>
In the present invention, one or more selected from the group of volatile antibacterial active compounds having a boiling point in the range of 100 to 240 ° C. is used as the volatile antibacterial active ingredient.
The compounds contained in the volatile antibacterial active compound group of the present invention preferably have a constituent carbon atoms in the range of 5 or more and 10 or less, and specific examples of suitable compounds include, for example, hinokithiol (boiling point:: 140 ° C), citronellal (boiling point: 204-206 ° C), green leaf aldehyde (trans-2-hexenal, boiling point: 146 ° C), citronellol (boiling point: 225 ° C), geraniol (boiling point: 229 ° C), nerol (boiling point: 224 ° C). ~ 225 ° C./745 mmHg) and the like. Of these, volatile antibacterial active compounds having a boiling point in the range of 100 to 200 ° C. are preferable, and hinokitiol and green leaf aldehyde are particularly preferable.
　本発明の揮散性抗菌活性成分層の形成については、使用する揮散性抗菌活性成分の形態や性質等に応じた手法を適宜選択することができる。例えば、室温で液体の揮散性抗菌活性成分であれば、希釈せずそのまま、基材フィルム層の一方の面上に塗布して揮散性抗菌活性成分層を形成することができる。室温で固体の揮散性抗菌活性成分や室温で液体の揮散性抗菌活性成分であっても、所定の溶媒、例えば、エタノール等により溶液を調製し、それを基材フィルム層の一方の面上に塗工し、溶媒を蒸散させることにより、実質的に揮散性抗菌活性成分のみからなる揮散性抗菌活性成分層を形成することもできる。また、揮散性抗菌活性成分を加熱して気化もしくは昇華して、基材フィルム層の一方の面上に付着させることにより、揮散性抗菌活性成分のみからなる揮散性抗菌活性成分層を形成する、蒸着処理方法を選択することもできる。
　本発明における揮散性抗菌活性成分層の厚さは、選択する揮散性抗菌活性成分の種類や、所望の抗菌活性維持期間により適宜決定すればよいが、通常、１μｍ以上５ｍｍ以下の範囲である。 For the formation of the volatile antibacterial active ingredient layer of the present invention, a method according to the form and properties of the volatile antibacterial active ingredient to be used can be appropriately selected. For example, if it is a volatile antibacterial active ingredient that is liquid at room temperature, it can be applied as it is on one surface of the base film layer without being diluted to form a volatile antibacterial active ingredient layer. Even if it is a volatile antibacterial active ingredient that is solid at room temperature or a volatile antibacterial active ingredient that is liquid at room temperature, a solution is prepared with a predetermined solvent, for example, ethanol, and the solution is placed on one surface of the base film layer. By coating and evaporating the solvent, a volatile antibacterial active ingredient layer consisting substantially only of the volatile antibacterial active ingredient can be formed. Further, by heating and vaporizing or sublimating the volatile antibacterial active ingredient and adhering it on one surface of the base film layer, a volatile antibacterial active ingredient layer composed of only the volatile antibacterial active ingredient is formed. The vaporization treatment method can also be selected.
The thickness of the volatile antibacterial active ingredient layer in the present invention may be appropriately determined depending on the type of the volatile antibacterial active ingredient to be selected and the desired antibacterial activity maintenance period, but is usually in the range of 1 μm or more and 5 mm or less.
＜揮散性抗菌活性成分透過層について＞
　本発明における揮散性抗菌活性成分透過層は、蒸着重合膜からなるものである。ここで蒸着重合膜とは、蒸着重合法に従って得られる薄膜を意味する。
　蒸着重合膜は、一般的に、加熱により蒸気化された二種以上の原料モノマーを、真空状態の成膜室内に導入し、成膜室内に配置された成膜対象物の表面に付着させ、かかる表面にて原料モノマー間の重合を進行させることによって、形成されるものである。すなわち、膜の形成が、本発明における揮散性抗菌活性成分層の表面に存在する、微細な凹凸に追従しながら進行することにより、揮散性抗菌活性成分透過層が形成されるため、揮散性抗菌活性成分層と揮散性抗菌活性成分透過層との間において優れた密着性を発揮する。また、蒸着重合膜は、極めて薄い膜厚においても作製することが可能であり、得られる蒸着重合膜は、不純物の含有が非常に少ないという利点をも有する。従って、本発明における徐放性抗菌フィルムは、揮散性抗菌活性成分層と揮散性抗菌活性成分透過層との間において、加水分解やヒートショック等に起因する層間剥離の発生が有利に抑制されるため、目的に応じた揮散性抗菌活性成分量を安定的に、放出し揮散させることが可能となる。 <About the volatile antibacterial active ingredient permeation layer>
The volatile antibacterial active ingredient permeable layer in the present invention is made of a vapor-deposited polymerized film. Here, the thin-film deposition polymer film means a thin film obtained according to the thin-film deposition polymerization method.
In the thin-film polymerization film, generally, two or more kinds of raw material monomers vaporized by heating are introduced into a film forming chamber in a vacuum state and adhered to the surface of a film forming object arranged in the film forming chamber. It is formed by advancing polymerization between raw material monomers on such a surface. That is, the formation of the film proceeds while following the fine irregularities existing on the surface of the volatile antibacterial active ingredient layer in the present invention, so that the volatile antibacterial active ingredient permeable layer is formed. It exhibits excellent adhesion between the active ingredient layer and the volatile antibacterial active ingredient permeation layer. Further, the thin-film vapor-deposited polymer film can be produced even with an extremely thin film thickness, and the obtained thin-film polymer film also has an advantage that the content of impurities is very small. Therefore, in the sustained release antibacterial film of the present invention, the occurrence of delamination due to hydrolysis, heat shock, etc. is advantageously suppressed between the volatilized antibacterial active ingredient layer and the volatilized antibacterial active ingredient permeation layer. Therefore, it is possible to stably release and volatilize the amount of volatilizing antibacterial active ingredient according to the purpose.
　本発明における揮散性抗菌活性成分透過層を構成する合成樹脂としては、従来から知られている蒸着重合法に従って膜形成が可能な合成樹脂の中から、揮散性抗菌活性成分に応じたものが適宜選択することができる。具体的には、揮散性抗菌活性成分透過層を構成する合成樹脂膜としては、ポリユリア樹脂膜、ポリアミド樹脂膜、ポリイミド樹脂膜、ポリアミドイミド樹脂膜、ポリエステル樹脂膜、ポリアゾメチン樹脂膜やポリウレタン樹脂膜等の、公知の蒸着重合法に従って作製可能な各種の合成樹脂膜を例示することができる。中でも、特に、ポリユリア樹脂膜は、揮散性抗菌活性成分が効果的に透過可能な架橋構造を有するため、有利に採用することができる。
　また、揮散性抗菌活性成分透過層の厚さは、揮散性抗菌活性成分のフィルム外部への単位時間当たりの放出量や、揮散性抗菌活性成分層に含まれる揮散性抗菌活性成分の種類や量等を総合的に考慮し、適宜に決定することができる。具体的には、揮散性抗菌活性成分透過層の厚さは、０．０１μｍ以上５０μｍ以下の範囲が好ましく、０．１μｍ以上１０μｍ以下の範囲がより好ましい。 As the synthetic resin constituting the volatile antibacterial active ingredient permeable layer in the present invention, among synthetic resins capable of forming a film according to a conventionally known vapor deposition polymerization method, those corresponding to the volatile antibacterial active ingredient are appropriately used. You can choose. Specifically, the synthetic resin film constituting the volatile antibacterial active ingredient permeable layer includes a polyurea resin film, a polyamide resin film, a polyimide resin film, a polyamideimide resin film, a polyester resin film, a polyazomethine resin film, and a polyurethane resin film. Various synthetic resin films that can be produced according to a known vapor deposition polymerization method such as, etc. can be exemplified. Above all, the polyyuria resin film can be advantageously adopted because it has a crosslinked structure in which the volatile antibacterial active ingredient can be effectively permeated.
The thickness of the volatile antibacterial active ingredient permeation layer is the amount of the volatile antibacterial active ingredient released to the outside of the film per unit time, and the type and amount of the volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer. Etc. can be comprehensively considered and determined as appropriate. Specifically, the thickness of the volatile antibacterial active ingredient permeation layer is preferably in the range of 0.01 μm or more and 50 μm or less, and more preferably in the range of 0.1 μm or more and 10 μm or less.
＜徐放性抗菌フィルムについて＞
　本発明における徐放性抗菌フィルムは、基材フィルム層の一方の面上に揮散性抗菌活性成分層が形成されており、さらに該揮散性抗菌活性成分層の面上に、蒸着重合膜からなる揮散性抗菌活性成分透過層が形成されている態様が好ましく、基材フィルム層、揮散性抗菌活性成分層および揮散性抗菌活性成分透過層の大きさが、概略同等であることが好ましい。
　本発明における徐放性抗菌フィルムは、農園芸作物低温保存用容器の上部に配されることが好ましく、当該容器内部の農園芸作物表面を覆う、または、当該容器天面部に貼付等により配されることがより好ましい。この場合、徐放性抗菌フィルムにおける揮散性抗菌活性成分透過層が、当該容器内部の農園芸作物に対向するように配することが好ましい。
　本発明の農園芸作物低温保存用容器は、「要件２」として、１ｃｍ２以上５，０００ｃｍ２以下の徐放性抗菌フィルムを備えることを特徴とするものである。徐放性抗菌フィルムの面積は、５ｃｍ２以上１，０００ｃｍ２以下のものが好ましく、１０ｃｍ２以上５００ｃｍ２以下のものがより好ましい。
　本発明の農園芸作物低温保存用容器に備える徐放性抗菌フィルムは、１枚でも良いし、２枚以上複数枚使用しても良い。複数枚使用する場合、本発明における徐放性抗菌フィルムの面積は、使用する全ての徐放性抗菌フィルムの面積の総和を意味する。 <About Sustained Release Antibacterial Film>
The sustained-release antibacterial film in the present invention has a volatile antibacterial active ingredient layer formed on one surface of the base film layer, and further comprises a vapor-deposited polymerized film on the surface of the volatile antibacterial active ingredient layer. It is preferable that the volatile antibacterial active ingredient permeable layer is formed, and the sizes of the base film layer, the volatile antibacterial active ingredient layer and the volatile antibacterial active ingredient permeable layer are substantially the same.
The sustained release antibacterial film in the present invention is preferably placed on the upper part of the container for low temperature storage of agricultural and horticultural crops, and is arranged by covering the surface of the agricultural and horticultural crop inside the container or by sticking to the top surface of the container. Is more preferable. In this case, it is preferable that the volatile antibacterial active ingredient permeation layer in the sustained release antibacterial film is arranged so as to face the agricultural and horticultural crops inside the container.
Agricultural and horticultural crops cryopreservation container according to the present invention, the "requirement 2" and is characterized in that it comprises 1 cm 2 or more 5,000 cm 2 or less sustained release antimicrobial film. Area of the sustained release antimicrobial film preferably has 5 cm 2 or more 1,000 cm 2 or less, and more preferably from 10 cm 2 or more 500 cm 2 or less.
The sustained release antibacterial film provided in the container for low temperature storage of agricultural and horticultural crops of the present invention may be one sheet, or two or more sheets may be used. When a plurality of sheets are used, the area of the sustained release antibacterial film in the present invention means the total area of all the sustained release antibacterial films used.
＜農園芸作物低温保存用容器について＞
　本発明の農園芸作物低温保存用容器は、樹脂製や紙製など素材や、袋形状、箱形状など形態は、特に限定するものではないが、中でも、箱形状のものが好適である。ただし、本発明における徐放性抗菌フィルムから揮散される揮散性抗菌活性成分量を維持できるように、ある程度密封可能な容器であることが好ましい。
　本発明の農園芸作物低温保存用容器は、本発明における徐放性抗菌フィルムから構成される容器であってもよいが、本発明における徐放性抗菌フィルムとは別の素材により構成される袋状のものも含む保存用容器に、農園芸作物を収容して、収容された農園芸作物の上部に本発明における徐放性抗菌フィルムを配置する方が簡便であり、コストの面からも有利である。
　本発明の農園芸作物低温保存用容器は、「要件１」として、その容積が２５ｃｍ３以上２５０，０００ｃｍ３以下であることを特徴とするものである。保存用容器の容積は、５００ｃｍ３以上１００，０００ｃｍ３以下のものが好ましく、１０００ｃｍ３以上５０，０００ｃｍ３以下のものがより好ましい。 <Containers for low temperature storage of agricultural and horticultural crops>
The container for low-temperature storage of agricultural and horticultural crops of the present invention is not particularly limited in terms of materials such as resin and paper, and shapes such as bag shape and box shape, but among them, box-shaped containers are preferable. However, it is preferable that the container can be sealed to some extent so that the amount of the volatilized antibacterial active ingredient volatilized from the sustained release antibacterial film in the present invention can be maintained.
The container for low-temperature storage of agricultural and horticultural crops of the present invention may be a container made of the sustained-release antibacterial film of the present invention, but a bag made of a material different from the sustained-release antibacterial film of the present invention. It is more convenient and cost-effective to store the agricultural and horticultural crops in a storage container including a container and place the sustained-release antibacterial film of the present invention on top of the contained agricultural and horticultural crops. Is.
Agricultural and horticultural crops cryopreservation container according to the present invention, the "requirement 1", and is characterized in that its volume is 25 cm 3 or more 250,000Cm 3 or less. The volume of storage container preferably has a 500 cm 3 or more 100,000 3 or less, 1000 cm 3 or more 50,000 cm 3 less is more preferable.
＜揮散性抗菌活性成分量について＞
　本発明の農園芸作物低温保存用容器は、保存用容器内の揮散性抗菌活性成分量を適正なものとすることができるため、揮散性抗菌活性成分による匂い移りや変色などで農園芸作物の品質が低下することなく、カビによる農園芸作物の商品価値の著しい低下を確実に抑制することができる。
　一般的に、密閉容器に徐放性抗菌フィルムを入れると、時間経過とともに、容器内の抗菌成分量は上昇する。容器内の抗菌成分量が少ないと十分な抗菌活性が得られず、農園芸作物が腐敗してしまう一方、容器内の抗菌成分量が多くなり過ぎると、揮散性抗菌活性成分の匂い移りや変色など農園芸作物の商品価値が低下してしまう。すなわち、カビによる農園芸作物の商品価値の著しい低下を確実に抑制し、かつ、揮散性抗菌活性成分による匂い移りのほか、変色などの品質劣化も抑制するためには、保存用容器内の抗菌成分量を適正な範囲にコントロールする必要がある。
　本発明は、保存用容器内の抗菌成分量を適正な範囲にコントロールできるものであり、そのために必要な徐放性抗菌フィルムの面積と保存用容器の容積の範囲および、徐放性抗菌フィルムと保存用容器との関係性を初めて特定したものである。 <About the amount of volatile antibacterial active ingredient>
In the container for low-temperature storage of agricultural and horticultural crops of the present invention, the amount of the volatile antibacterial active ingredient in the storage container can be adjusted to an appropriate level. It is possible to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold without deteriorating the quality.
Generally, when a sustained release antibacterial film is placed in a closed container, the amount of antibacterial component in the container increases with the passage of time. If the amount of antibacterial ingredient in the container is too small, sufficient antibacterial activity cannot be obtained and the agricultural and horticultural crops will rot. The commercial value of agricultural and horticultural crops will decline. That is, in order to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold, and to suppress quality deterioration such as discoloration as well as odor transfer due to volatile antibacterial active ingredients, antibacterial in the storage container. It is necessary to control the amount of ingredients within an appropriate range.
The present invention can control the amount of antibacterial component in the storage container within an appropriate range, and the area of the sustained-release antibacterial film required for that purpose, the range of the volume of the storage container, and the sustained-release antibacterial film. This is the first time that the relationship with the storage container has been identified.
　本発明における揮散性抗菌活性成分は、沸点が１００～２４０℃の範囲にある揮散性抗菌活性化合物群から選択される１種以上のものであることも、上記保存用容器内の抗菌成分量を適正なものとすることを可能とする要件の１つである。
　以上のとおり、本発明の農園芸作物低温保存用容器内の揮散性抗菌活性成分量を適正なものとすることにより、カビによる農園芸作物の商品価値の著しい低下を確実に抑制し、かつ、抗菌活性成分による匂い移りのほか、変色などの品質劣化をさせることのない、流通や保存に適した農園芸作物低温保存用容器とすることができるものである。 The volatile antibacterial active ingredient in the present invention may be one or more selected from the volatile antibacterial active compound group having a boiling point in the range of 100 to 240 ° C. It is one of the requirements that makes it possible to make it proper.
As described above, by optimizing the amount of volatile antibacterial active ingredient in the container for low temperature storage of agricultural and horticultural crops of the present invention, it is possible to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold, and also. It can be used as a container for low-temperature storage of agricultural and horticultural crops suitable for distribution and storage without causing quality deterioration such as discoloration in addition to odor transfer due to antibacterial active ingredients.
　本発明の農園芸作物低温保存用容器内の揮散性抗菌活性成分量を、適正なものとするためには、下記要件１～３を満たすことが必要である。
［要件１］；保存用容器の容積が２５ｃｍ３以上２５０，０００ｃｍ３以下である。
［要件２］；徐放性抗菌フィルムの面積が１ｃｍ２以上５，０００ｃｍ２以下である。
［要件３］；保存用容器の容積（ｃｍ３）に対する、徐放性抗菌フィルムの面積（ｃｍ２）の比が、０．０２以上である。
　上記「要件３」について説明する。
　「要件３」は、保存用容器の容積（ｃｍ３）に対する、徐放性抗菌フィルムの面積（ｃｍ２）の比が、すなわち、徐放性抗菌フィルムの面積（ｃｍ２）を、保存用容器の容積（ｃｍ３）で除した値が、０．０２以上とするものである。
　本発明の農園芸作物低温保存用容器内の揮散性抗菌活性成分量を、適正なものとするためには、特に、この「要件３」を満たすことが重要である。この「要件３」の比が０．０２より小さい場合には、農園芸作物低温保存用容器内の揮散性抗菌活性成分量が不足し、保存用容器内の農園芸作物に対する防カビ効果を得ることができない。「要件３」の比を０．０２以上とすることにより、カビによる農園芸作物の商品価値の著しい低下を確実に抑制し、かつ、抗菌活性成分による匂い移りのほか、変色などの品質劣化をさせることのない、流通や保存に適した農園芸作物低温保存用容器とすることが可能となる。 In order to make the amount of volatile antibacterial active ingredient in the container for low temperature storage of agricultural and horticultural crops of the present invention appropriate, it is necessary to satisfy the following requirements 1 to 3.
[Requirement 1]; volume of storage container is 25 cm 3 or more 250,000Cm 3 or less.
[Requirement 2]; the area of the sustained release antimicrobial film is 1 cm 2 or more 5,000 cm 2 or less.
[Requirement 3]; The ratio of the area of the sustained release antibacterial film (cm 2 ) to the volume of the storage container (cm 3 ) is 0.02 or more.
The above "requirement 3" will be described.
"Requirements 3" to volume of storage container (cm 3), the ratio of the area of the sustained release antimicrobial film (cm 2), i.e., the area of controlled release antimicrobial film (cm 2), for storage containers The value divided by the volume (cm 3 ) of is 0.02 or more.
In order to make the amount of the volatile antibacterial active ingredient in the container for low temperature storage of agricultural and horticultural crops of the present invention appropriate, it is particularly important to satisfy this "Requirement 3". When the ratio of this "Requirement 3" is less than 0.02, the amount of the volatile antibacterial active ingredient in the container for low temperature storage of agricultural and horticultural crops is insufficient, and the antifungal effect on the agricultural and horticultural crops in the container for storage is obtained. Can't. By setting the ratio of "Requirement 3" to 0.02 or more, it is possible to surely suppress a significant decrease in the commercial value of agricultural and horticultural crops due to mold, and to prevent quality deterioration such as discoloration as well as odor transfer due to antibacterial active ingredients. It is possible to make a container for low-temperature storage of agricultural and horticultural crops suitable for distribution and storage without causing it to occur.
　以下、実施例を挙げて本発明を説明するが、本発明の技術範囲はこれらにより限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the technical scope of the present invention is not limited thereto.
 ＜徐放性抗菌フィルムの調製＞
　揮散性抗菌活性化合物であるヒノキチオールを、ロール・ツー・ロール（roll to roll）方式の蒸着重合膜形成装置を用いて、ポリエチレンテレフタレート（ＰＥＴ）製フィルム（厚さ：１２μｍ）上に、有効成分量が１．３ｍｇ/ｃｍ２となるように揮散性抗菌活性成分層を形成した。次いで、同じ蒸着重合膜形成装置を用いて、ポリユリア樹脂からなる蒸着重合膜を作製した。ポリユリア樹脂からなる蒸着重合膜は、厚さ：４μｍにて作製した。 <Preparation of sustained release antibacterial film>
Amount of active ingredient of hinokithiol, which is a volatile antibacterial active compound, on a polyethylene terephthalate (PET) film (thickness: 12 μm) using a roll-to-roll type vapor-deposited polymerized film forming apparatus. A volatile antibacterial active ingredient layer was formed so as to have a concentration of 1.3 mg / cm 2. Next, a thin-film polymer film made of a polyureia resin was produced using the same thin-film polymer film-forming apparatus. The thin-film polymerized film made of polyureia resin was prepared with a thickness of 4 μm.
 ＜農園芸作物低温保存に関する試験１＞
　保存用容器として、中敷きザル付きの密閉容器１（容量：１，１００ｃｍ３、底面サイズ：外寸１５０ｍｍ×１３４ｍｍ、高さ：外寸７７ｍｍ）を使用した。図１に示すように、保存用容器の底面に蒸留水（２０ｍＬ）を浸したペーパータオルを敷いて、湿度を保持できるようにし（図１中の１）、中敷きザルには包装用スポンジ載置し（図１中の２）、保存用容器の蓋部内側に調製した徐放性抗菌フィルム１（面積：７８ｃｍ２）を両面テープにより貼り（図１中の３）、使用した。上記保存用容器は、本発明における「要件３」が約０．０７１である。
　保存する農園芸作物として、シャインマスカットの果粒を使用した。図１に示すように、包装用スポンジ載置した中敷きザルに１２粒を入れ（図１中の４のように）、滅菌水を噴霧した後、風乾したものを使用した。これを、図１中の１にセットして蓋（図１中の３）を閉めたものを実施例１として保存試験を行った。
　徐放性抗菌フィルムを使用しない点でのみ相違する保存用容器を比較例１として、同様の保存試験を行った。
　保存開始から１週間毎に観察し、各試験区に発生した腐敗果を確認し、その数をカウントした。なお、腐敗果は観察確認時に取り除いた。
　保存試験は、それぞれ３回実施して、累積腐敗果率（％）の平均値を算出した。　表１に、保存温度５℃における試験結果をまとめて示す。 <Test 1 for low temperature storage of agricultural and horticultural crops>
As a storage container, a closed container 1 with an insole colander (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm × 134 mm, height: outer dimensions 77 mm) was used. As shown in FIG. 1, a paper towel soaked in distilled water (20 mL) is laid on the bottom surface of the storage container so that the humidity can be maintained (1 in FIG. 1), and a packaging sponge is placed on the insole colander. (2 in FIG. 1), a sustained-release antibacterial film 1 (area: 78 cm 2 ) prepared inside the lid of the storage container was attached with double-sided tape (3 in FIG. 1) and used. The storage container has "Requirement 3" in the present invention of about 0.071.
Shine Muscat berries were used as the agricultural and horticultural crops to be preserved. As shown in FIG. 1, 12 grains were placed in an insole colander on which a packaging sponge was placed (as shown in 4 in FIG. 1), sterilized water was sprayed, and then air-dried was used. This was set to 1 in FIG. 1 and the lid (3 in FIG. 1) was closed, and a preservation test was conducted as Example 1.
A similar storage test was performed using a storage container that differs only in that it does not use a sustained release antibacterial film as Comparative Example 1.
The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
The storage test was carried out three times each, and the average value of the cumulative spoilage rate (%) was calculated. Table 1 summarizes the test results at a storage temperature of 5 ° C.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すとおり、本発明の農園芸作物低温保存用容器（実施例１）は、保存開始から７０日間（２．５カ月間）経過しても腐敗果が全く無く、保存開始から９１日間（３カ月以上）経過後の累積腐敗果率の平均が１１．１％であった。また、保存開始から９１日経過後の果粒は、揮散性抗菌活性成分による匂い移りや変色などの品質劣化は確認されなかった。これに対して、本発明のものとは異なる保存用容器を使用した場合（比較例１）では、保存開始から２１日間（３週間）経過した時点で累積腐敗果率の平均が８．３％であり、９１日間（３カ月以上）経過後には６９．４％に達した。
　すなわち、本発明の農園芸作物低温保存用容器を使用することにより、高価であり商品価値の高いシャインマスカットの様な農園芸作物のカビによる腐敗を、有効に抑制し得ることが明らかとなった。
　一方、詳細な試験データは省略するものの、本発明の農園芸作物低温保存用容器を使用して、本発明の低温の定義から外れる２０℃で保存した場合、２１日（３週間）までに果粒表面に褐色の斑点が現れ、その後４９日（７週間）までに全ての果粒の腐敗が確認された。この結果は、本発明の農園芸作物低温保存用容器を使用しても、低温保存以外の条件下では、抗菌活性成分による変色などの品質劣化が発生し、その後、腐敗が助長されることを示唆するものと考えている。 As shown in Table 1, the container for low-temperature storage of agricultural and horticultural crops (Example 1) of the present invention had no putrefactive fruits even after 70 days (2.5 months) from the start of storage, and 91 days from the start of storage. The average cumulative spoilage rate after (3 months or more) was 11.1%. In addition, no quality deterioration such as odor transfer or discoloration due to the volatile antibacterial active ingredient was confirmed in the fruit grains 91 days after the start of storage. On the other hand, when a storage container different from that of the present invention was used (Comparative Example 1), the average cumulative spoilage rate was 8.3% after 21 days (3 weeks) from the start of storage. After 91 days (3 months or more), it reached 69.4%.
That is, it has been clarified that by using the container for low temperature storage of agricultural and horticultural crops of the present invention, it is possible to effectively suppress the spoilage of agricultural and horticultural crops such as Shine Muscat, which is expensive and has high commercial value, due to mold. ..
On the other hand, although detailed test data is omitted, when the container for low temperature storage of agricultural and horticultural crops of the present invention is used and stored at 20 ° C., which deviates from the definition of low temperature of the present invention, the result is by 21 days (3 weeks). Brown spots appeared on the grain surface, and by 49 days (7 weeks) thereafter, rotting of all the grains was confirmed. The result is that even if the container for low temperature storage of agricultural and horticultural crops of the present invention is used, quality deterioration such as discoloration due to the antibacterial active ingredient occurs under conditions other than low temperature storage, and then putrefaction is promoted. I think it suggests.
＜農園芸作物低温保存に関する試験２＞
　上記「農園芸作物低温保存に関する試験１」と同じ中敷きザル付きの密閉容器１（容量：１，１００ｃｍ３、底面サイズ：外寸１５０ｍｍ×１３４ｍｍ、高さ：外寸７７ｍｍ）に果粒１２粒と徐放性抗菌フィルム１（面積：７８ｃｍ２）を、同様の容器２（容量：５，０００ｃｍ３、底面サイズ：外寸２１３ｍｍ×２６３ｍｍ、高さ：外寸１３０ｍｍ）に果粒２５粒と徐放性抗菌フィルム２（面積：３１２ｃｍ２）を、それぞれ使用して、上記「農園芸作物低温保存に関する試験１」と同様にセットした。
　保存する農園芸作物として、灰色かび病菌分生子懸濁液（１０６個／ｍＬ）を噴霧接種した後、風乾したシャインマスカットの果粒を使用し保存温度５℃における保存試験を行った。なお、容器１（実施例２、比較例２）は蒸留水（２０ｍＬ）を、容器２（実施例３、比較例３）は蒸留水（１００ｍＬ）を用いて湿度を保持した。
　保存開始から１週間毎に観察し、各試験区に発生した腐敗果を確認し、その数をカウントした。なお、腐敗果は観察確認時に取り除いた。
　保存試験は、実施例２、比較例２が５回、実施例３、比較例３は４回実施して、累積腐敗果率（％）の平均値を算出した。
　表２に、試験結果をまとめて示す。 <Test 2 for low temperature storage of agricultural and horticultural crops>
12 fruit grains in a closed container 1 (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm x 134 mm, height: outer dimensions 77 mm) with an inlay colander, which is the same as the above "Test 1 for low temperature storage of agricultural and horticultural crops". Sustained release of antibacterial film 1 (area: 78 cm 2 ) into a similar container 2 (capacity: 5,000 cm 3 , bottom size: outer dimensions 213 mm x 263 mm, height: outer dimensions 130 mm) with 25 fruit grains. The sex antibacterial film 2 (area: 312 cm 2 ) was set in the same manner as in the above-mentioned "Test 1 on low temperature storage of agricultural and horticultural crops".
As an agricultural and horticultural crop to be preserved, a suspension of Botrytis cinerea conidia (106 cells / mL) was spray-inoculated, and then a preservation test was conducted at a preservation temperature of 5 ° C. using air-dried Shine Muscat berries. The humidity was maintained in the container 1 (Example 2 and Comparative Example 2) using distilled water (20 mL) and in the container 2 (Example 3 and Comparative Example 3) using distilled water (100 mL).
The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
The storage test was carried out 5 times in Example 2 and Comparative Example 2, and 4 times in Example 3 and Comparative Example 3, and the average value of the cumulative putrefaction rate (%) was calculated.
Table 2 summarizes the test results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　この「農園芸作物低温保存に関する試験２」は、強制的に灰色かび病菌を接種する非常に厳しい環境を模した、保存試験である。
　表２に示すとおり、本発明とは異なる保存用容器である比較例２は、保存開始から２８日目に試験果粒の全てが、同じく本発明とは異なる保存用容器である比較例３では、試験果粒の９８％が腐敗した。
　一方、このような非常に厳しい条件下の保存試験においても、本発明の農園芸作物低温保存用容器（実施例２、３）では、農園芸作物のカビによる腐敗は試験果粒の概略５分の１以下程度に留まり、特に、実施例３では試験果粒の６％と、腐敗抑制効果に極めて優れていることが明らかとなった。また、この優れた腐敗抑制効果は「要件１」の保存用容器の容積の違いに関わらず、発揮されることが明らかとなった。
　また、実施例２、３の保存開始から２８日経過後の果粒は、抗菌活性成分による匂い移りや変色などの品質劣化は確認されなかった。 This "test 2 on low temperature storage of agricultural and horticultural crops" is a preservation test that imitates a very harsh environment in which Botrytis cinerea is forcibly inoculated.
As shown in Table 2, in Comparative Example 2 which is a storage container different from the present invention, in Comparative Example 3 in which all the test berries are also different from the present invention on the 28th day from the start of storage. , 98% of the test grains rotted.
On the other hand, even in the storage test under such extremely strict conditions, in the container for low-temperature storage of agricultural and horticultural crops of the present invention (Examples 2 and 3), the decay of the agricultural and horticultural crop by mold is approximately 5 minutes of the test fruit grains. In particular, in Example 3, it was found that 6% of the test berries were extremely excellent in the effect of suppressing spoilage. Further, it was clarified that this excellent anti-corruption effect is exhibited regardless of the difference in the volume of the storage container of "Requirement 1".
In addition, no quality deterioration such as odor transfer or discoloration due to the antibacterial active ingredient was confirmed in the berries 28 days after the start of storage of Examples 2 and 3.
＜農園芸作物低温保存に関する試験３＞
　上記「農園芸作物低温保存に関する試験１」と同じ中敷きザル付きの密閉容器１（容量：１，１００ｃｍ３、底面サイズ：外寸１５０ｍｍ×１３４ｍｍ、高さ：外寸７７ｍｍ）に果粒１２粒、徐放性抗菌フィルム１（面積：７８ｃｍ２）、徐放性抗菌フィルム３（面積：３９ｃｍ２）、徐放性抗菌フィルム４（面積：１９ｃｍ２）をそれぞれ使用し、上記「農園芸作物低温保存に関する試験１」と同様にセットし、蒸留水（２０ｍＬ）を用いて湿度を保持した。
　保存する農園芸作物として、灰色かび病菌分生子懸濁液（１０６個／ｍＬ）を噴霧接種した後、風乾したシャインマスカット果粒を使用し温度５℃における保存試験を行った。
　保存開始から１週間毎に観察し、各試験区に発生した腐敗果を確認し、その数をカウントした。なお、腐敗果は観察確認時に取り除いた。
　保存試験は、それぞれ４回実施して、累積腐敗果率（％）の平均値を算出した。
　表３に、試験結果をまとめて示す。 <Test 3 for low temperature storage of agricultural and horticultural crops>
12 fruit grains in a closed container 1 (capacity: 1,100 cm 3 , bottom size: outer dimensions 150 mm x 134 mm, height: outer dimensions 77 mm) with an inlay colander, which is the same as the above "Test 1 for low temperature storage of agricultural and horticultural crops". The sustained release antibacterial film 1 (area: 78 cm 2 ), the sustained release antibacterial film 3 (area: 39 cm 2 ), and the sustained release antibacterial film 4 (area: 19 cm 2 ) were used, respectively, and the above-mentioned "low temperature storage of agricultural and horticultural crops" was used. The film was set in the same manner as in "Test 1", and the humidity was maintained using distilled water (20 mL).
As an agricultural and horticultural crop to be preserved, a suspension of Botrytis cinerea conidia (106 cells / mL) was spray-inoculated, and then a preservation test was conducted at a temperature of 5 ° C. using air-dried Shine Muscat grains.
The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
The storage test was carried out four times each, and the average value of the cumulative spoilage rate (%) was calculated.
Table 3 summarizes the test results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　この「農園芸作物低温保存に関する試験３」は、強制的に灰色かび病菌を接種する非常に厳しい環境を模した、保存試験である。
　表３に示すとおり、本発明とは異なる保存用容器である比較例５は、保存開始から２８日目において、試験果粒の９７．９％が腐敗した。
　一方、このような非常に厳しい条件下の保存試験においても、本発明の農園芸作物低温保存用容器（実施例４、５）では、農園芸作物のカビによる腐敗は、保存開始から７０日（２．５カ月）経過後においても、試験果粒の概略３０％以下に留まり、腐敗抑制効果に極めて優れていることが明らかとなった。
　一方、比較例４は、本発明における「要件３」、すなわち保存用容器の容積（ｃｍ３）に対する、徐放性抗菌フィルムの面積（ｃｍ２）の比が約０．０１７であるため、本発明の保存用容器とは相違する。そのため、比較例４での保存では、保存開始から２８日目以降の農園芸作物のカビによる腐敗の進行が、実施例の２．５～４倍程度にまで進むことが確認された。 This "test 3 on low temperature storage of agricultural and horticultural crops" is a preservation test that imitates a very harsh environment in which Botrytis cinerea is forcibly inoculated.
As shown in Table 3, in Comparative Example 5, which is a storage container different from the present invention, 97.9% of the test berries were putrefactive on the 28th day from the start of storage.
On the other hand, even in the storage test under such extremely strict conditions, in the container for low temperature storage of agricultural and horticultural crops (Examples 4 and 5) of the present invention, the decay of agricultural and horticultural crops due to mold is 70 days from the start of storage (Examples 4 and 5). Even after the lapse of 2.5 months), it remained at about 30% or less of the test berries, and it was clarified that the effect of suppressing putrefaction was extremely excellent.
On the other hand, Comparative Example 4 has "Requirement 3" in the present invention, that is, the ratio of the area of the sustained release antibacterial film (cm 2 ) to the volume of the storage container (cm 3 ) is about 0.017. It differs from the storage container of the invention. Therefore, in the preservation in Comparative Example 4, it was confirmed that the progress of mold rot of agricultural and horticultural crops after the 28th day from the start of preservation progressed to about 2.5 to 4 times that of the Example.
＜農園芸作物低温保存に関する試験４＞
　中敷きザル付きの密閉容器３（容量：０．００３０ｍ３、底面サイズ：外寸２３９ｍｍ×１７６ｍｍ、高さ：外寸９１ｍｍ）に果粒４１粒を入れ、徐放性抗菌フィルム５（面積：２３３ｃｍ２）、徐放性抗菌フィルム１（面積：７８ｃｍ２）それぞれを使用し、上記「農園芸作物低温保存に関する試験１」と同様に、滅菌水を噴霧接種（無接種）した後、風乾した果粒について、表４に示す保存温度における保存試験を行った。なお、容器３は蒸留水（６０ｍＬ）を用いて湿度を保持した。
　保存開始から１週間毎に観察し、各試験区に発生した腐敗果を確認し、その数をカウントした。なお、腐敗果は観察確認時に取り除いた。
　保存試験は、それぞれ３回実施して、累積腐敗果率（％）の平均値を算出した。
　表４に、試験結果をまとめて示す。なお、比較例８、９は、保存開始から２１日目の結果において、実施例６、７と大きな差が出たことからこれ以上の経過観察は必要ないと判断し試験を終了した。表４中「－」は、試験観察を実施しなかったことを意味する。 <Test 4 for low temperature storage of agricultural and horticultural crops>
Put 41 berries in a closed container 3 with an inoculation colander (capacity: 0.0030 m 3 , bottom size: outer dimensions 239 mm x 176 mm, height: outer dimensions 91 mm), and release the sustained-release antibacterial film 5 (area: 233 cm 2). ), Sustained release antibacterial film 1 (area: 78 cm 2 ), spray-inoculated with sterilized water (no inoculation), and then air-dried fruit grains in the same manner as in "Test 1 for low-temperature storage of agricultural and horticultural crops". Was subjected to a storage test at the storage temperature shown in Table 4. The humidity of the container 3 was maintained by using distilled water (60 mL).
The plants were observed every week from the start of storage, and the number of rotten fruits generated in each test plot was confirmed and counted. The rotten fruit was removed at the time of observation confirmation.
The storage test was carried out three times each, and the average value of the cumulative spoilage rate (%) was calculated.
Table 4 summarizes the test results. In Comparative Examples 8 and 9, the results on the 21st day from the start of storage showed a large difference from Examples 6 and 7, so it was judged that no further follow-up was necessary, and the test was terminated. “-” In Table 4 means that the test observation was not performed.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４に示すとおり、本発明の農園芸作物低温保存用容器（実施例６、７）は、一般的な保存状態を模した灰色かび病菌の無接種保存において、本発明のものとは異なる保存用容器（比較例６、７）に比べて、農園芸作物のカビによる腐敗抑制効果に極めて優れていることが明らかとなった。また、実施例６、７の保存開始から２８日経過後の果粒は、抗菌活性成分による匂い移りや変色などの品質劣化は確認されなかった。
　一方、本発明の低温の定義から外れる２３℃で保存した場合（比較例８、９）、徐放性抗菌フィルムを使用（比較例８）しても、カビによる腐敗抑制効果が得られないことも明らかとなった。さらに、比較例８において、保存開始から約１０日目で変色がみられた。この結果は、本発明の農園芸作物低温保存用容器を使用しても、低温保存以外の条件下では、抗菌活性成分による変色などの品質劣化が発生し、その後、腐敗が助長されることを示唆するものと考えている。 As shown in Table 4, the container for low-temperature storage of agricultural and horticultural crops (Examples 6 and 7) of the present invention is different from that of the present invention in non-inoculation storage of gray mold fungi imitating a general storage state. It was clarified that the effect of suppressing mold spoilage of agricultural and horticultural crops was extremely excellent as compared with the containers for use (Comparative Examples 6 and 7). In addition, no quality deterioration such as odor transfer or discoloration due to the antibacterial active ingredient was confirmed in the berries 28 days after the start of storage of Examples 6 and 7.
On the other hand, when stored at 23 ° C., which deviates from the definition of low temperature of the present invention (Comparative Examples 8 and 9), even if a sustained release antibacterial film is used (Comparative Example 8), the effect of suppressing mold spoilage cannot be obtained. Was also revealed. Further, in Comparative Example 8, discoloration was observed about 10 days after the start of storage. The result is that even if the container for low temperature storage of agricultural and horticultural crops of the present invention is used, quality deterioration such as discoloration due to the antibacterial active ingredient occurs under conditions other than low temperature storage, and then putrefaction is promoted. I think it suggests.
　本発明の容器に備えられている徐放性抗菌フィルムは、揮散性抗菌活性成分透過層が蒸着重合膜により構成されていることから、揮散性抗菌活性成分層に含有される特定の揮散性抗菌活性化合物を安定的に放出させることが可能であり、保存用容器の容積（要件１）と当該徐放性抗菌フィルムの面積（要件２）とを特定の範囲のものとし、さらに当該容積に対する当該面積の比を特定の数値以上（要件３）とすることにより、保存用容器内の揮散した抗菌活性成分量を適正なものとすることができる。これらの相乗効果により、農園芸作物の品質を低下させることなく、カビによる農園芸作物の商品価値の著しい低下を確実に抑制することができ非常に有用である。 In the sustained-release antibacterial film provided in the container of the present invention, since the volatile antibacterial active ingredient permeable layer is composed of a vapor-deposited polymerized film, a specific volatile antibacterial active ingredient contained in the volatile antibacterial active ingredient layer. It is possible to stably release the active compound, and the volume of the storage container (requirement 1) and the area of the sustained-release antibacterial film (requirement 2) are within a specific range, and the volume is further increased. By setting the area ratio to a specific value or more (Requirement 3), the amount of volatilized antibacterial active ingredient in the storage container can be made appropriate. Due to these synergistic effects, it is very useful because it is possible to surely suppress a significant decrease in the commercial value of the agricultural and horticultural crops due to mold without deteriorating the quality of the agricultural and horticultural crops.

Claims (3)

  1. 　基材フィルム層と、
    　沸点が１００～２４０℃の範囲にある揮散性抗菌活性化合物群から選択される１種以上を含有する揮散性抗菌活性成分層と、
    　蒸着重合膜からなる揮散性抗菌活性成分透過層を、
    　この順で積層してなる徐放性抗菌フィルムを備え、かつ、
    　下記要件１～３を満たす農園芸作物低温保存用容器。
    ［要件１］；保存用容器の容積が２５ｃｍ３以上２５０，０００ｃｍ３以下である。
    ［要件２］；徐放性抗菌フィルムの面積が１ｃｍ２以上５，０００ｃｍ２以下である。
    ［要件３］；保存用容器の容積（ｃｍ３）に対する、徐放性抗菌フィルムの面積（ｃｍ２）の比が、０．０２以上である。     Base film layer and
    A volatile antibacterial active ingredient layer containing at least one selected from the volatile antibacterial active compound group having a boiling point in the range of 100 to 240 ° C.
    A volatile antibacterial active ingredient permeable layer made of a vapor-deposited polymerized film.
    It is equipped with a sustained release antibacterial film laminated in this order, and
    A container for low-temperature storage of agricultural and horticultural crops that meets the following requirements 1 to 3.
    [Requirement 1]; volume of storage container is 25 cm 3 or more 250,000Cm 3 or less.
    [Requirement 2]; the area of the sustained release antimicrobial film is 1 cm 2 or more 5,000 cm 2 or less.
    [Requirement 3]; The ratio of the area of the sustained release antibacterial film (cm 2 ) to the volume of the storage container (cm 3 ) is 0.02 or more.
  2. 　請求項１に記載の低温保存用容器に農園芸作物を収容してなる、農園芸作物収容包装体。 A farming and horticultural crop storage package for storing agricultural and horticultural crops in the low-temperature storage container according to claim 1.
  3. 　請求項１に記載の保存用容器を用いて農園芸作物を収容して、－３℃以上１５℃以下で保存する、農園芸作物の保存方法。
          A method for preserving agricultural and horticultural crops, wherein the agricultural and horticultural crops are stored using the storage container according to claim 1 and stored at -3 ° C. or higher and 15 ° C. or lower.
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JP2017226188A (en) * 2016-06-24 2017-12-28 小島プレス工業株式会社 Sustained-release film

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